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PH sensor using nano electrodes in organic semiconductor

Article in Conference proceedings: ... Annual International Conference of the IEEE Engineering in Medicine and Biology Society. IEEE Engineering in Medicine and Biology Society. Conference ·
February 2004
DOI: 10.1109/IEMBS.2004.1403581 · Source: PubMed

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Proceedings of the 26th Annual International Conference of the IEEE EMBS
San Francisco, CA, USA • September 1-5, 2004

pH Sensor using Nano Electrodes in Organic Semiconductor

Xiaoshan Zhu and Chong H. Ahn
BioMEMS and MicroSystem Lab
Department of Electrical & Computer Engineering and Computer Science
University of Cincinnati, OH, USA

Abstract— A new pH sensor using nano electrodes in
organic semiconductor P3HT (regioregular poly(3-
hexylthiophene)) has been designed, fabricated and
characterized in this work. In this sensor, the organic
semiconductor is directly exposed to pH sample solution,
and an electrical field is applied to drive the protons in
the solution to the polymer surface. The accumulated
protons at the interface between organic semiconductor
and solution change the electron density at organic
semiconductor surface, so that the conductivity of the
organic semiconductor film is modulated. In order to
improve the sensitivity of sensor, P3HT is coated on the
interdigitated array nanoelectrodes, and the conductivity
of P3HT between two bands of electrodes is measured
for pH characterization. A good conductivity
modulation by the proton concentration or pH value is
shown in the sensor testing.
Keywords—pH Detection, P3HT, Conductivity, Nanoelectrodes
I. INTRODUCTION
Recently organic semiconductor has been gaining a
popular attention in the research and industry application
due to its low-cost manufacturing, disposability and easy
processing. The so-far great application achievement of
organic semiconductor in optoelectronic devices, such as
light emitting diode and battery, is motivating researchers to
extend the application areas of organic semiconductor [1-4].
As a result, nowadays more and more interests are paid on
organic semiconductor transducers.
Some pioneering works have been reported to use
organic semiconductor field-effect transistor (FET) as the
sensing device for gas or pH value. L. Torsi reported a gas
sensor using organic semiconductor FET. Gas interacts with
the organic semiconductor and modulates the carrier
mobility of organic semiconductor. Therefore, the current-
voltage curves of organic semiconductor FET is
characterized for gas sensing [5-7]. C. Bartic reported to use
an organic ion-selective field-effect transistor (ISFET) to
measure pH value of sample solution [8]. His device adopts
the conventional detection mechanism that pH variation
causes the potential drop across the dielectric and
semiconductor interface, but the working semiconductor in
his device is polymer instead of silicon. Although these
pioneering works are based on organic semiconductor field-
effect transistor, one fact has to be pointed out that organic
semiconductor has really low carrier mobility when
compared to silicon. Thus, these organic semiconductor
FETs and their based sensors usually work under large
voltage range. In order to operate polymer FET in low
voltage, people tried to deposit high dielectric material
(instead of SiO2) as the insulating layer [9], or to build
nanochannel for FET using nanofabrication technology [10-
11]. Processing the high dielectric material needs high cost,
and nano polymer FET requires the complex small-current
detection circuit.
In this work, we adopts organic semiconductor in pH
measurement using a different approach. In our approach,
the organic semiconductor is directly exposed to pH sample
solution, and an electrical field is established to be vertical
to the organic semiconductor surface, and drives the protons
in the solution to the polymer surface. The accumulated
protons at the interface between polymer and solution
change the electron density at polymer surface, so that the
conductivity of organic semiconductor film is modulated.
Based on this concept, a conductivity-measured pH sensor
has been designed, fabricated, and characterized for a wide
pH value range (pH = 2 – 12) in this work. The experiment
results show a good conductivity modulation by the proton
concentration or pH value.
II. METHOD AND DESIGN
Figure 1 illustrates the cut view and the operation of the
pH sensor. The sensor is built on Si/SiO2 substrate. The
sensing window is exposed to sample solution. The
operation of sensor includes the following steps. First, an
Ag/AgCl
Electrolyte
V
Si
Polymer
Conductivity
SiO2 Measurement
Au
Figure 1. Cut view and operation of proposed device for pH
measurement: (1) Applying an electrical field between pH solution and
Si substrate for a few seconds; (2) Measure the semiconductive polymer
conductivity between two electrodes after removing the electrical field.

0-7803-8439-3/04/$20.00©2004 IEEE 1968

electrical field is generated to be vertical to the polymer
surface by applying a potential between Si substrate and the
reference electrode. In this step, protons are supposed to be
driven to the polymer surface to form the interface charge.
Second, the polymer conductivity between two electrodes is
measured and recorded. Every time before applying new
sample solution to the sensing window, the sensing window
is washed using the neutral buffer (pH = 7) and nitrogen
repeatedly. In addition, considering the slow oxidization of
P3HT in the air by oxygen, all measurements are done in
nitrogen environment.
C6H13 MicroPad Nanoelectrodes
MicroPad
S dissolved in chloroform (0.8% wt), is spin-coated on the
S n
Si/SiO2
C6H13
(a) (b)
Figure 2. (a) Molecular structure of P3HT (regioregular poly(3-
hexylthiophene-2,5-diyl); (b) Structure of elelctrodes
Organic semiconductor P3HT (regioregular poly(3-
hexylthiophene-2,5-diyl)) is used in this pH sensor. P3HT is
soluble to chloroform, and can be spin-coated on the wafer
surface in the processing. Moreover, it has the highest
carrier mobility as one of conjugated polymers, and has
good ohmic contact with gold layer. It has been widely used
in organic semiconductor FET [12-13]. The molecular
structure of P3HT is shown in Figure 2(a). In order to
improve the sensitivity of sensor, the electrodes are designed
as the interdigitated array. In this array, the spacing between
two electrodes is in submicrons (~ 0.5 um), and the width
for each electrode finger is around 200 nm. The structure of
all electrodes is presented in Figure 2(b). The pH sensing
part is the interdigitated array nanoelectrodes and the coated
P3HT on nanoelectrodes, and two big electrode pads are
used for electrical connection in measurement.
II. FABRICATION
The designed device is fabricated using mixed-match
processing steps, which consists of nanofabrication and
microfabrication.
First, PMMA (Microchem, 495K) with a 300 nm
thickness is spin-coated at the oxidized silicon surface, and
then the nanopatterns are exposed by e-beam (Raith 150 e-
beam lithography system). After the development of the
exposed PMMA, Ti/Au (100 Å/ 1000 Å) layer is deposited
on the patterned sample surface, and then dipped into
acetone for lift-off.
After the nanofabrication, the connection pads are
fabricated using the UV-light-lithography-based lift-off
1969
techniques, as the following steps. First, the positive
photoresist (Shipley 1818) is coated on the substrate with
3000 rpm, and then the wafer is baked in the 90 ºC oven for
30 minutes. Second, the baked Shipley 1818 is exposed
under UV light (300 nm ~ 460 nm wavelength, ~7 mJ/cm2)
for 10 seconds, and consequently is immersed in
chlorobenzene for 45 seconds. After immersion, dry the
sample in the 120 ºC oven for 30 seconds. Third, the sample
is developed for 1 minute and dry. Fourth, Ti/Au (100 Å/
1000 Å) layer is deposited on the patterned sample surface.
Finally, the deposited sample is baked at 120 ºC for 1 – 2
hours and then dipped into acetone for lift-off.
In the last step, organic semiconductor P3HT
(regioregular poly(3-hexylthiophene-2,5-diyl)), which is
electrode surface at 1500 rpm speed. After the coating,
the sensing window is covered and sealed by a small piece
of PDMS membrane, and the other coated P3HT film is
etched using RIE (Ar). In the testing, the pH solution is
dropped in the sensing window.
The whole processing steps are graphically illustrated
in Figure 3. Figure 4(a) shows the photo graphics of
fabricated nanoelectrodes and microelectrodes, and a SEM
graphics for a close view on the interdigitated array
nanoelectrodes is presented in Figure 4(b). The thickness of
the coated P3HT on nanoelectrode surface is measured
using profilometer, and the thickness data is shown in
Figure 5.
PMMA
(a) PR coating (f) UV lithography
(b) E-beam lithography (g) Metal deposition
Microelectrode
(c) Metal deposition (h) Micro Lift-off
Nanoelectrodes
Cover membrane
(d) Nano Lift-off (l) P3HT coating and RIE(Ar)
S1818
P3HT
(e) PR coating (m) Remove PDMS
Figure 3. Mixed-match processing: (a) – (d) E-beam lithography for
lift-off of nanoelectrodes; (e) – (h) UV-light lithography for lift-off of
microelectrodes; (l) – (m) P3HT coating and patterning
 III. MEASUREMENT RESULTS
Microelectrode 100 um
A. Preparation of pH sample solution and Ag/AgCl
electrode

The neutral sample solution (pH=7) is PBS buffer

Nanoelectrodes
(a) Photo graphics of interdigitated array electrodes
purchased from Scientific Fisher. The PBS buffer includes
0.1 M choride ions, which makes sure the reference
elelctrode (Ag/AgCl) is stable after immersing into pH
sample solution. The other sample solutions with different
pH values are prepared by modulate the neutral sample
solution with HCl acid or potassium hydroxide.
The reference electrode is made by slowly depositing a
layer of AgCl onto a segment of clean silver wire by
electrolysis. A clean silver wire and a clean Pt film
respectively are connected to the positive and negative
polarities of current source, and then immerse them in 0.1 M
KCl solution with a 10 mA/cm2 current density for 60
seconds. A blackish deposit of AgCl will be deposited on
the silver wire. Before using, the reference electrode is
stored in a dilute solution of saline.

B. Conductivity measurement

The conductivity of organic semiconductor between two

electrodes is measured using a digital multimeter (DMM).
All measurement is done in nitrogen environment. Figure 6
shows the conductivity change before and after applying pH
sample solution on the senmiconductive polymer. Before
dropping pH sample solution, the resistant between two
electrodes are huge (~68 Mohms). But after applying pH
(b) SEM graphics of interdigitated array electrodes in nao scale
sample solution on the organic semiconductor surface, the
resistant drops off dramatically. Although the resistant for
Figure 4. Fabricated electrode strucuture using mixed-mathc different pH sample solutions varies, the variation is not
processing: Photo (a) and SEM (b) graphics. The dimension of obvious and the resistance is around 3 Mohms. The reason
electrode fingers is ~ 80 nm and its spacing is ~ 500 nm.
for this dramatic conductivity change possibly is that ions in
3500 the sample solution change the electron density of organic
semiconductor surface, and thus cause the huge variation of
3000 conductivity.
Scanning range: 3 mm
Thickness (Angstrom)

In order to check the effect of proton/hydroxyl

2500 Scanning speed: 100 um/s concentration (or different pH values) on polymer
Sampling rate: 200 Hz
conductivity, a 10 V potential is added between the Si
2000
substrate and the reference electrode, which is immersed in
1500
pH sample solution. The electrical field between Si
substrate and the reference electrode lasts for 30-second
1000 duration, and then the polymer conductivity is measured
Thickness = ~ 1600 Å
again. Figure 7 gives the comparison of two cases: with
500 electrical field excitation and without electrical field
excitation. From Figure 7, it can be seen that the high
0 concentration proton causes a higher conductivity, while the
0 1000 2000 3000 4000 5000 6000 high concentration hydroxyl results a lower conductivity.
Sample points The detailed physic mechanism for this phenomenon is still
Figure 5. The measured thickness of P3HT using profilometer. under investigation. One intuitive explanation is that
The scanning range is 3 mm, the scanning speed is 100 um/s, and electrical field drives the protons to the polymer surface to
the sampling rate is 200 Hz. further increase the polymer surface electron density, so that

1970
 the conductivity becomes larger for the sample solution with sensor, but various pH-detecting based sensors. Compared
smaller pH values or higher proton concentration. to the organic semiconductor FET based sensors, the
application using such a property avoids the low carrier
0.5 mobility and the complex bias circuit and small-current
detection circuit.
0.4
With pH solution ACKNOWLEDGMENT
Conductivity (uS)

0.3 The authors thank National Science Foundation (NSF)

for the funding on Raith-150 e-beam lithography system at
University of Cincinnati, and also thank Mr. Ron Flenniken
0.2 Dramatic change in University of Cincinnati for his technical assistance in the
metal deposition.
0.1
Without pH solution
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